JPH10298439A - Stabilizer for resin and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stabilizer which shows high effect of stabilizing especially a polyolefin resin and a chlorinated resin against both thermal deterioration and photooxidative deterioration by using a salt of a hindered amine with phosphoric acid, phosphorous acid or an ester thereof as the effective ingredient. SOLUTION: This stabilizer contains a hindered amine salt represented by general formula I or general formula II (wherein R<1> and R<2> are each independently hydrogen atoms, alkyls, alkenyls, cycloalkyls, aryls or the like; R<3> is hydrogen, hydroxyl, oxygen, nitroso, an alkyl, an alkenyl, a hydroxyalkyl, an aryl or the like; R<4> s are independently hydrogen atoms or alkyls; and n is a number of 1-3) as the effective ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel hindered amine salt as an active ingredient for a resin and its use, and more particularly, to improving the stability of the resin against both thermal aging and photo-oxidative degradation. The present invention relates to a stabilizer for a resin containing a hindered amine salt as an active ingredient, and its use, particularly as a stabilizer against heat aging and photo-oxidative degradation of resins such as chlorine-containing resins and polyolefin resins.

[0002]

2. Description of the Related Art Conventionally, typically, resins such as chlorine-containing resins such as polyvinyl chloride resins and polyolefin resins such as polyethylene and polypropylene are subjected to heat, light, oxygen, or the like during processing or use. It is known that, under the influence of such factors, the product is deteriorated with phenomena such as molecular breakage and molecular cross-linking, and further, softening, embrittlement, and discoloration, and the commercial value thereof is significantly impaired. Conventionally, in order to solve the problem of such thermal degradation and photo-oxidation degradation of the resin, by blending various phosphorus compounds, hindered piperidine compounds, phenolic antioxidants, ultraviolet absorbers and the like into the resin, It is known that the stabilization can be achieved.

In particular, it has been well known that a phosphorus compound and a hindered piperidine compound are used in combination so that a resin is stable against both heat deterioration and photo-oxidation deterioration, and more recently, For example, JP-A-6-2200
No. 75, Japanese Unexamined Patent Application Publication No. 7-285981, Japanese Unexamined Patent Application Publication No.
As described in -16873 and the like, some organic phosphorus compounds having a hindered piperidinyl group in the molecule have been proposed as stabilizers for resins. Further, JP-A-4-11660 and JP-A-4-59852 disclose that a salt of a compound having a hindered piperidinyl group and an organic phosphorus compound is effective in preventing thermal deterioration and photo-oxidative deterioration of a resin. It is stated that there is.

[0004]

However, these conventionally known stabilizers still have insufficient stabilizing effects, and the present invention has been made to solve such a problem. And a resin stabilizing agent comprising a novel hindered amine salt comprising a hindered amine and a phosphorus compound as an active ingredient, which simultaneously exhibits a high stabilizing effect against both thermal degradation and photo-oxidative degradation of the resin. And the use thereof, and in particular, to provide a resin composition containing an effective amount of such a stabilizer and a method of stabilizing the resin by incorporating an effective amount of such a stabilizer. .

[0005]

According to the present invention, as a first resin stabilizer, a compound represented by the general formula (I):

[0006]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms, Represents an aryl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, a polyoxyalkylenealkyl group or a polyoxyalkylenearyl group having an alkenyl group of 18. R ³ represents a hydrogen atom, a hydroxyl group, an oxygen atom, a nitroso group. An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms, 2 to 18 carbon atoms Of an aryl group having an alkenyl group, an alkoxyalkyl group, a polyoxyalkylene aryl group or an alkyl group The number represents the acyl group is 1 to 18, when R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms .R ¹ and R ² are both hydrogen atoms, n represents 1 3 represents R ¹ and R ²
Is a hydrogen atom, n represents a number of ^{1 to 2, and} when both R ¹ and R ² are not hydrogen atoms, n represents 1. ) Which comprises a hindered amine salt represented by the formula (1) as an active ingredient.

According to the present invention, as the second resin stabilizer, a compound represented by the general formula (II):

[0009]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms, Represents an aryl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, a polyoxyalkylenealkyl group or a polyoxyalkylenearyl group having an alkenyl group of 18. R ³ represents a hydrogen atom, a hydroxyl group, an oxygen atom, a nitroso group. An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms, 2 to 18 carbon atoms Of an aryl group having an alkenyl group, an alkoxyalkyl group, a polyoxyalkylene aryl group or an alkyl group The number represents the acyl group is 1 to 18, when R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms .R ¹ and R ² are both hydrogen atoms, n represents 1 3 represents R ¹ and R ²
Is a hydrogen atom, n represents a number of ^{1 to 2, and} when both R ¹ and R ² are not hydrogen atoms, n represents 1. ) Which comprises a hindered amine salt represented by the formula (1) as an active ingredient.

Further, according to the present invention, there is provided a stabilized resin composition obtained by blending the above-mentioned resin stabilizer with a resin, and a method of stabilizing a resin wherein the above-mentioned resin stabilizer is blended with a resin. Provided.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First of the stabilizers for resins according to the present invention
Comprises the first hindered amine salt represented by the general formula (I) as an active ingredient. According to the present invention,
In the first hindered amine salt represented by the general formula (I), R ¹ and R ² are preferably
Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, or 6 to 18 carbon atoms;
R ³ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and R ⁴ is preferably
An alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group.

The first hindered amine salt according to the present invention can be prepared, for example, by adding a compound represented by the general formula (III) in an appropriate organic solvent:

[0014]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms, An aryl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, a polyoxyalkylenealkyl group or a polyoxyalkylenearyl group having 18 alkenyl groups. (IV)

[0016]

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(Wherein R ³ represents a hydrogen atom, a hydroxyl group, an oxygen atom, a nitroso group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, An aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms, an aryl group having an alkenyl group having 2 to 18 carbon atoms, an alkoxyalkyl group, a polyoxyalkylene aryl group or an alkyl group having 1 to 1 carbon atoms;
8 represents an acyl group, and R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ) Is mixed with the hindered piperidinol derivative at a required ratio according to the raw materials used, if necessary, while heating, and then the organic solvent is distilled off to obtain crystals. be able to. The above hindered piperidinol derivative is generally used in an equivalent amount or less based on the hydroxyl group of the phosphoric acid or the organic phosphoric acid ester.

As the hindered piperidinol derivative, 2,2,6,6-tetramethylpiperidinol or 1,2,2,6,6-pentamethylpiperidinol is preferably used. Further, as the organic solvent, in particular,
Although not limited, preferably, methanol is used.

The second aspect of the resin stabilizer according to the present invention comprises a hindered amine salt represented by the above general formula (II) as an active ingredient. According to the present invention, in the second hindered amine salt represented by the general formula (II), R ¹ and R ² are preferably each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 3 to 2 carbon atoms
0 is an alkenyl group or an aryl group having 6 to 18 carbon atoms, and R ³ is preferably a hydrogen atom or 1 to 20 carbon atoms.
, Particularly preferably an alkyl group having 1 to 4 carbon atoms, and R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

The second hindered amine salt according to the present invention is also similar to the first hindered amine salt, for example, for example,
Formula (V) in an appropriate organic solvent

[0021]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms, An aryl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, a polyoxyalkylenealkyl group or a polyoxyalkylenearyl group having 18 alkenyl groups). The hindered piperidinol derivative represented by the general formula (IV) is mixed with the hindered piperidinol derivative at a required ratio under heating if necessary according to the raw materials used, and then the organic solvent is distilled off. Thus, it can be obtained as crystals. The above hindered piperidinol derivative is generally used in an equivalent amount or less based on the hydroxyl group of the phosphorous acid or the organic phosphite.

Also in this case, preferably, the hindered piperidinol derivative is 2,2,6,6-tetramethylpiperidinol or 1,2,2,6,6-pentamethylpiperidinol. It is preferably used, and the organic solvent is not particularly limited, but preferably, methanol is used.

The resin stabilizer according to the present invention contains such a hindered amine salt as an active ingredient, and is particularly useful as a stabilizer for a resin which is easily degraded by the action of heat, light or oxygen. Such resins include various thermoplastic and thermosetting resins, and accordingly, the stabilizers according to the present invention include various chemicals based on these resins,
For example, in addition to films and sheets, various molded products, paints,
It is useful as a stabilizer for adhesives, waxes, lubricating oils and the like.

In particular, the resin stabilizer according to the present invention includes, among the above resins, polyvinyl chloride resin, chlorinated vinyl chloride resin, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer resin, and vinyl chloride-vinylidene chloride copolymer. Chlorine-containing resin such as polymerized resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin, polyethylene resin such as low density polyethylene, high density polyethylene, linear low density polyethylene and polypropylene resin etc. It is useful as a stabilizer for a representative polyolefin resin, particularly useful as a stabilizer for polyvinyl chloride resin, polyethylene resin or polypropylene resin.

Further, the stabilizer for resin according to the present invention includes, for example, polystyrene, polyurethane, polycarbonate,
Polyester, epoxy resin, unsaturated polyester resin, ethylene / acrylate copolymer resin, acrylonitrile / styrene copolymer resin, acrylonitrile /
It is also useful as a stabilizer for butadiene / styrene copolymer resins, methacrylic resins and the like.

The stabilizer for a resin according to the present invention, particularly, for the paint, for example, a stabilizer for urethane resin paint, acrylic resin paint, vinyl resin paint, polyester resin paint, epoxy resin paint, aminoalkyl resin paint and the like. It is also useful.

When the stabilizer for a resin according to the present invention is blended with a resin as a stabilizer to obtain a stabilized resin composition, the blending amount is usually 0.01 to 5 parts by weight based on 100 parts by weight of the resin.
It is in the range of parts by weight.

According to the present invention, the hindered amine salt comprises
The stoichiometric salt may not necessarily be used, and the phosphate or phosphite forming the hindered amine salt may be composed of a mixture of a monoester and a diester. And a salt of a mixture of a phosphite and a piperidinol derivative. Of course, the piperidinol derivative forming the hindered amine salt does not need to be a single compound, for example, 2,2,6,6-tetramethylpiperidinol and 1,2,2,
It may be a mixture with 6,6-pentamethylpiperidinol.

In preparing such a stabilized resin composition according to the present invention, a conventional compounding agent may be appropriately compounded depending on the use and characteristics of the resin composition. Examples of such a compounding agent include a plasticizer, a reinforcing agent, a processing aid, a heat stabilizer, a coloring inhibitor, a metal soap, a lubricant, a flame retardant, a nucleating agent, a metal deactivator, an antistatic agent, Pigments, inorganic fillers, organic phosphates, organic phosphites, surfactants, antioxidants, ultraviolet absorbers, conventionally known hindered amine light stabilizers, plate-out inhibitors, epoxy compounds, etc. Can be mentioned.

[0031]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

Synthesis Example 1

[0033]

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The hindered amine salt represented by the following formula (Table 1)
In the four-necked flask, 2,3
77.1 g of 2,6,6-tetramethylpiperidinol was added to 100 mL of methanol, and dissolved by stirring. Next, 14.7 g of phosphoric acid was dissolved in 30 mL of methanol,
This solution was added dropwise to the solution of 2,2,6,6-tetramethylpiperidinol and reacted.

After this, the reaction mixture obtained is heated to a temperature of 60
The methanol was distilled off using an evaporator on a hot water bath at 90 ° C. to obtain 90.0 g of the desired product as white crystals. Similarly, hindered amine salts shown in Table 1 were prepared. The melting points and elemental analysis values are shown in Tables 1 and 2.

In addition to those shown in Table 1, Table 3
And various hindered amine salts and the like shown in Table 5 were prepared and used as resin stabilizers in the following Examples and Comparative Examples. In Tables 1, 3 and 4, A represents 2, 2, 6,
6-tetramethylpiperidinol or 1,2,2,6,6-pentamethylpiperidinol; B represents phosphoric acid, phosphoric acid ester, phosphorous acid or phosphite, and these in a hindered amine salt Is shown by A: B. In Table 5, A represents a conventionally known hindered amine compound, X, Y or Z, and a part thereof was used as a phosphite.

(Preparation of Stabilized Polypropylene Resin Composition and Evaluation of Its Stability) The hindered amine salts shown in Tables 3 and 4 (and the conventional ones) were added to a base formulation comprising 100 parts by weight of polypropylene and 0.1 part by weight of calcium stearate. 0.1 part by weight of the following hindered amine compound X, Y or Z), which is known as a stabilizer, is added.
After calendering at ℃, a test press sheet was produced at 170 ℃. However, in Table 4, in the case of Nos. 25 and 26, 0.2 parts by weight was used.

[0038]

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[0039]

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[0040]

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The test press sheet was evaluated for weather resistance and heat resistance. Tables 3 and 4 show the obtained results. ◎ indicates very good, ○ indicates good, Δ indicates slightly bad, and × indicates bad.

(Weather Resistance) The test press sheet was placed in a sunshine weather meter (light source carbon arc), the black panel temperature was 83 ° C., and the spray cycle was 18
The light was irradiated under the condition of min / 120 min, and the surface state after the light irradiation for 500 hours was visually judged. (Heat resistance) The discoloration degree when the test press sheet was left in a gear oven at 160 ° C. for 10 days was visually determined.

(Preparation of stabilized polyvinyl chloride resin composition and evaluation of its stability) Polyvinyl chloride resin (degree of polymerization = 1)
000) 100 parts by weight, 50 parts by weight of di-2-ethylhexyl phthalate (DOP), 3 parts by weight of epoxidized soybean oil, 0.5 parts by weight of barium stearate and 0.3 parts by weight of zinc stearate. 2 to 0.1 of a hindered amine salt shown in Table 3 (and a mixture of the hindered amine compound X, Y or Z conventionally known as a stabilizer) were added, and calendering was performed at 160 ° C. A 0.3 mm test film was produced. However, in Table 4, in numbers 25 and 26, 0.2
Parts by weight were used.

The test film was evaluated for weather resistance and heat resistance. Tables 2 and 3 show the obtained results. ◎ is very good, ○ is good, △ is slightly bad,
X indicates bad.

(Weather Resistance) The test film was exposed outdoors for one year, and the degree of discoloration was visually determined. (Heat resistance) Put the above test film in a gear oven
The degree of discoloration when heated at 80 ° C. for 70 minutes was visually determined.

COMPARATIVE EXAMPLE As shown in Table 5, compounds X, Y or Z conventionally known as stabilizers or phosphites thereof (molar ratio 1: 1) were used as stabilizers. As in the example,
A polypropylene resin composition and a vinyl chloride resin composition were prepared, and their heat resistance and weather resistance were evaluated in the same manner as in the examples. Table 5 shows the results.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

As described above, the resin stabilizer containing the hindered amine salt according to the present invention as an active ingredient is particularly suitable for blending it with a resin such as a chlorine-containing resin or a polyolefin-based resin, so as to reduce the heat degradation and light A high stabilizing effect can be given to oxidative deterioration.

Continued on the front page (72) Inventor Hideo Tsujimoto 5-1 Ebisshima-cho, Sakai-shi, Osaka Sakai Chemical Industry Co., Ltd. Sakai Works Co., Ltd. (72) Inventor Katsuharu Miyata 5-1-1 Ebisshima-cho, Sakai City, Osaka Sakai Chemical Industry Co., Ltd.

Claims (8)

[Claims] 1. A compound of the general formula (I) (Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms,
An aryl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, a polyoxyalkylenealkyl group or a polyoxyalkylenearyl group having an alkenyl group having 2 to 18 carbon atoms is shown. R ³ represents a hydrogen atom, a hydroxyl group, an oxygen atom, a nitroso group, a carbon number of 1 to 20;
Alkyl group, alkenyl group having 3 to 20 carbon atoms, hydroxyalkyl group having 2 to 4 carbon atoms, aryl group, 1 carbon atom
Aryl group having an alkyl group of from 18 to 18, having 2 to 1 carbon atoms
An aryl group having 8 alkenyl group, an alkoxyalkyl group, the carbon number of the polyoxyalkylene aryl group or an alkyl group or an acyl group is 1 to 18, R ⁴ is
Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. When R ¹ and R ² are both hydrogen atoms, n
Represents a number of 1 to 3, and when any of R ¹ and R ² is a hydrogen atom, n represents a number of ^{1 to 2. When} both R ¹ and R ² are not a hydrogen atom, n represents 1 Show. A resin stabilizer comprising a hindered amine salt represented by the formula (1) as an active ingredient. 2. A compound of the general formula (II) (Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aryl group having an alkyl group having 1 to 18 carbon atoms,
An aryl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, a polyoxyalkylenealkyl group or a polyoxyalkylenearyl group having an alkenyl group having 2 to 18 carbon atoms is shown. R ³ represents a hydrogen atom, a hydroxyl group, an oxygen atom, a nitroso group, a carbon number of 1 to 20;
Alkyl group, alkenyl group having 3 to 20 carbon atoms, hydroxyalkyl group having 2 to 4 carbon atoms, aryl group, 1 carbon atom
Aryl group having an alkyl group of from 18 to 18, having 2 to 1 carbon atoms
An aryl group having 8 alkenyl group, an alkoxyalkyl group, the carbon number of the polyoxyalkylene aryl group or an alkyl group or an acyl group is 1 to 18, R ⁴ is
Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. When R ¹ and R ² are both hydrogen atoms, n
Represents a number of 1 to 3, and when either R ¹ or R ² is a hydrogen atom, n represents a number of ^{1 to 2. When} both R ¹ and R ² are not hydrogen atoms, n represents 1 Show. A resin stabilizer comprising a hindered amine salt represented by the formula (1) as an active ingredient. 3. A method for stabilizing a resin, comprising adding an effective amount of the stabilizer according to claim 1 to the resin. 4. A stabilized resin composition obtained by blending an effective amount of the stabilizer according to claim 1 or 2 with a resin. 5. The stabilized resin composition according to claim 4, wherein the resin is a thermoplastic resin. 6. The stabilized resin composition according to claim 5, wherein the thermoplastic resin is a chlorine-containing resin. 7. The stabilized resin composition according to claim 5, wherein the thermoplastic resin is a polyolefin resin. 8. The stabilized resin composition according to claim 6, wherein the chlorine-containing resin is a polyvinyl chloride resin.